JP2781033B2 - Metal oxide material - Google Patents
Metal oxide materialInfo
- Publication number
- JP2781033B2 JP2781033B2 JP1307440A JP30744089A JP2781033B2 JP 2781033 B2 JP2781033 B2 JP 2781033B2 JP 1307440 A JP1307440 A JP 1307440A JP 30744089 A JP30744089 A JP 30744089A JP 2781033 B2 JP2781033 B2 JP 2781033B2
- Authority
- JP
- Japan
- Prior art keywords
- plane
- present
- oxide material
- temperature
- superconducting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は銅の酸化物材料、特に超伝導材料として有利
な銅酸化物材料又は該材料を少なくとも一部含有する超
伝導材料に関する。Description: TECHNICAL FIELD The present invention relates to a copper oxide material, particularly a copper oxide material which is advantageous as a superconducting material or a superconducting material containing at least a part of the material.
（従来の技術） 従来、銅の酸化物のなかで超伝導性材料としては、主
にLn2−xAxCuO4（Lnはランタノイド元素、ＡはCa、Sr、
Ce又はBa）、LnBa2Cu3Oy（Lnはランタノイド元素）、Bi
2Sr2CanCu1+nOy（ｎ＝０、１、２）、T1aBa2CanCu1+nOy
（ａ＝１、２、ｎ＝０〜４）及びPb2Sr2Ca1-xLnxCu3Oy
（Lnはランタノイド元素）の組成式で表される材料が知
られている。The superconducting material among the (prior art) prior, oxides of copper, mainly Ln 2 - x A x CuO 4 (Ln is a lanthanoid element, A is Ca, Sr,
Ce or Ba), LnBa 2 Cu 3 O y (Ln is a lanthanoid element), Bi
2 Sr 2 Ca n Cu 1 + n O y (n = 0,1,2), T1 a Ba 2 Ca n Cu 1 + n O y
(A = 1, 2, n = 0-4) and Pb 2 Sr 2 Ca 1-x Ln x Cu 3 O y
A material represented by a composition formula of (Ln is a lanthanoid element) is known.
（発明が解決しようとしている問題点） しかしながら、これらの銅酸化物をその用途に従って
焼結体や薄膜にする場合には、反応温度として900乃至
1,000℃付近という高温が必要であり、製造コストが高
くなったり、基板がかなり限定される等の問題点があ
り、製造プロセス的に工業化が不可能に近かった。(Problems to be Solved by the Invention) However, when these copper oxides are formed into a sintered body or a thin film according to the intended use, a reaction temperature of 900 to 900 is required.
A high temperature of about 1,000 ° C. is required, and there are problems such as a high manufacturing cost and a considerably limited number of substrates, and the industrialization of the manufacturing process is almost impossible.
又、上記Bi系やTl系の材料の場合には、臨界電流値が
低い、パッキングが弱い、重金属の割合が多く、その分
危険度が高い等の問題があり、実用化には不十分であっ
た。Further, in the case of the Bi-based or Tl-based materials, there are problems such as a low critical current value, weak packing, a large proportion of heavy metals, and a high degree of danger, which are insufficient for practical use. there were.
従って本発明の目的は、生成時の反応温度が低くて済
み、又、焼結性の良い新規な銅酸化物材料を提供するこ
とにある。Accordingly, an object of the present invention is to provide a novel copper oxide material which requires a low reaction temperature at the time of formation and has good sinterability.
本発明の他の目的は、臨界電流の高い新規な超伝導性
銅酸化物材料を提供することにある。Another object of the present invention is to provide a novel superconducting copper oxide material having a high critical current.
本発明の更に他の目的は、重金属の比率が小さい超伝
導材料として有用な銅酸化物材料を提供することにあ
る。Still another object of the present invention is to provide a copper oxide material useful as a superconducting material having a low ratio of heavy metals.
本発明の更に他の目的は、液体ヘリウムで容易に冷却
出来る超伝導材料として有利な新規な銅酸化物材料を提
供することにある。特に従来技術ではBi、Sr、Cu、Ｏの
元素のみではTcが8Kまでしか上がらなかった。又、それ
にランタノイドを置換したBi2Sr2-xLnxCuOyでもTcは20K
までしか上がらなかった。Still another object of the present invention is to provide a novel copper oxide material which is advantageous as a superconducting material which can be easily cooled with liquid helium. In particular, in the prior art, Tc increased only up to 8K only with the elements of Bi, Sr, Cu, and O. In addition, Tc is 20K even with Bi 2 Sr 2-x Ln x CuO y substituted with lanthanoid.
I only went up.
（問題点を解決する為の手段） 上記目的は以下の本発明によって達成される。(Means for Solving the Problems) The above object is achieved by the present invention described below.
即ち、本発明は、ｃ軸に垂直な原子配列を有する面か
らなる層状の酸化物材料において、ｃ軸に沿って順にAO
面、AO面、BO面、CuO2面、CO面、DO面、CO面、CuO2面、
BO面、AO面となる周期構造を有し、上記Ａ及びＤが、Bi
及びTlからなる元素群から選ばれた１種以上の元素又は
原子団であり、Ｂ及びＣがSr及びBaからなる元素群から
選ばれた１種以上の元素又は原子団であることを特徴と
する金属酸化物材料である。That is, the present invention relates to a layered oxide material comprising a plane having an atomic arrangement perpendicular to the c-axis, wherein AO is sequentially arranged along the c-axis.
Plane, AO plane, BO plane, CuO 2 plane, CO plane, DO plane, CO plane, CuO 2 plane,
It has a periodic structure of BO and AO planes, and A and D are Bi
And at least one element or atomic group selected from the element group consisting of Tl, and B and C are at least one element or atomic group selected from the element group consisting of Sr and Ba. Metal oxide material.
（作用） 銅酸化物の構造において、特定の層状構造とし、且つ
特定の金属イオンを用いることにより、優れた超伝導性
を発揮する銅酸化物材料が提供される。(Function) By using a specific layered structure and a specific metal ion in the structure of the copper oxide, a copper oxide material exhibiting excellent superconductivity is provided.
尚、本発明においては、例えば、AO面と記する場合、
Ａイオンと酸素イオンの中心が必しも正確に同一平面上
にある必要はない。つまり、Ａイオンの中心と酸素イオ
ンの中心の面が若干ずれていたり、又、モジュレーショ
ンによって面全体がうねっている場合もあり得る。又、
AO面におけるＡイオン又は酸素イオンは若干（１乃至２
割）の欠陥を含んでいる場合があり得る。又、特に酸素
イオンは10割欠陥する面がある場合もここではAO面とす
る。In the present invention, for example, when described as AO surface,
The centers of the A ion and the oxygen ion need not necessarily be exactly on the same plane. That is, the plane of the center of the A ion and the center of the oxygen ion may be slightly displaced, or the entire plane may undulate due to modulation. or,
A ion or oxygen ion on the AO surface is slightly (1 to 2
%) Defects. In particular, even if there is a surface where oxygen ions have a defect of 100%, the surface is referred to as an AO surface here.
（好ましい実施状態様） 本発明の銅酸化物材料は前記構造を有する限りいずれ
のものでもよい。(Preferred Embodiment State) The copper oxide material of the present invention may be any as long as it has the above structure.
上記本発明の銅酸化物材料を作成する方法としては、
所謂セラミックス材料で一般に使われている様な原料粉
末からの加熱による反応及び焼結法がいずれも本発明に
おいて使用可能である。As a method for producing the copper oxide material of the present invention,
Any of the reaction and sintering by heating from raw material powder as generally used in so-called ceramic materials can be used in the present invention.
この様な方法の例は、Material Research Bulletin第
８巻777頁（1973年）、Solid State Communication第17
巻27頁（1975年）、Zeitschrift fur Physik B第64巻18
9頁（1986年）、Physical Review Letters第58巻第９号
908頁（1987年）等に示されており、これらの方法は現
在では定性的には極めて一般的な方法として知られてい
る。Examples of such methods are described in Material Research Bulletin, Vol. 8, p. 777 (1973), Solid State Communication, Vol.
Volume 27 (1975), Zeitschrift fur Physik B 64:18
9 pages (1986), Physical Review Letters Vol. 58, No. 9
908 (1987), etc., and these methods are now qualitatively known as extremely general methods.
又、原料粉末を高温で溶融してから単結晶成長させる
方法も本発明において有用である。更に原料を含むター
ゲットを用いた高周波スパッタリングやマグネトロンス
パッタリング等のスパッタリング法、電子ビーム蒸着、
その他の真空蒸着法或いはクラスターイオンビーム法や
原料にガス材を使うCVD法又はプラズマCVD法等を使って
支持体上に本発明の材料を薄膜状に形成してもよい。こ
の様な場合には気体の酸素を装置内に送り込んで装置内
で酸化させることが効果的な場合が多い。より具体的な
製造条件の例は後記実施例において説明する。Further, a method of melting a raw material powder at a high temperature and then growing a single crystal is also useful in the present invention. Further, sputtering methods such as high-frequency sputtering and magnetron sputtering using a target containing raw materials, electron beam evaporation,
The material of the present invention may be formed into a thin film on a support by other methods such as a vacuum evaporation method, a cluster ion beam method, a CVD method using a gas material as a raw material, or a plasma CVD method. In such a case, it is often effective to send gaseous oxygen into the apparatus and oxidize it in the apparatus. More specific examples of the manufacturing conditions will be described in Examples below.
この様にして得られた本発明の銅酸化物材料は、金属
−非金属転移を示さず、室温では10-4乃至100Ωcm程度
の電気抵抗を持ち、30乃至80K前後の温度で超伝導状態
を示す。Copper oxide materials of the present invention obtained in this manner, metal - do not exhibit non-metallic transition has an electrical resistance of about 10 -4 to 10 0 [Omega] cm at room temperature, superconducting at 30 to 80K temperature of about Indicates the status.
前記組成式において、Cuサイトの他の遷移金属元素又
は０（酸素）サイトにClやＦ等の元素が数％含まれてい
ても今回発見した超伝導銅酸化物の特性と大きく劣化さ
せることはなかった。In the above composition formula, even if a transition metal element other than the Cu site or an element such as Cl or F is contained in the 0 (oxygen) site by several percent, the properties of the superconducting copper oxide discovered this time are not significantly deteriorated. Did not.
又、本発明で使用する原料は全て安価なものであり、
原料コストは低く本発明の材料は安価に提供可能であ
る。例えば、本発明の材料はYBa2Cu3O7-zで代表される
一連の化合物に比べてむしろ安価に提供出来る。又、上
記の化合物に比べて本発明の材料は空気中において比較
的安定で劣化が少なく、湿度による劣化も比較的少な
い。Also, the raw materials used in the present invention are all inexpensive,
The raw material cost is low, and the material of the present invention can be provided at low cost. For example, the material of the present invention can be provided at a lower cost than a series of compounds represented by YBa 2 Cu 3 O 7-z . In addition, compared to the above compounds, the material of the present invention is relatively stable in air, has little deterioration, and has relatively little deterioration due to humidity.
又、Bi2Sr2CuOyに比べ、重金属元素であるBiの比率が
著しく小さくなり、製品としての安定性が高められたば
かりでなく、超伝導転移温度も液体ヘリウム温度（4.2
K）よりも30K以上高いので、比較的手軽に且つ安定的に
超伝導材料として使用することができる。Also, compared to Bi 2 Sr 2 CuO y , the ratio of Bi, which is a heavy metal element, is remarkably reduced, and not only the stability as a product is improved, but also the superconducting transition temperature is the liquid helium temperature (4.2%).
Since it is higher than K) by 30 K or more, it can be used relatively easily and stably as a superconducting material.
又、材料生成時の反応温度も800℃以下と低く抑える
ことが可能で焼結性もよい。従って薄膜にする際には非
常に有利である。Further, the reaction temperature at the time of material generation can be suppressed to 800 ° C. or less, and sinterability is good. Therefore, it is very advantageous in forming a thin film.
（実施例） 次に実施例を挙げて本発明を更に具体的に説明する。(Examples) Next, the present invention will be described more specifically with reference to examples.
実施例１ 原料としてBi2O3、Tl2O3、SrCO3、BaCO3及びCuOを用
い、これらを（Bi、Tl、Sr、Ba元素）対Cuの比を約7:2
に秤量して乾式混合した。これらの混合物を夫々φ10m
m、厚み1mmのペレット状に加圧形成し、生成物を夫々ア
ルミナボートの上で720乃至820℃で大気中若しくは酸素
中で反応及び焼結させ、本発明の胴酸化物材料を調製し
た。Example 1 Bi 2 O 3 , Tl 2 O 3 , SrCO 3 , BaCO 3 and CuO were used as raw materials, and the ratio of (Bi, Tl, Sr, Ba element) to Cu was about 7: 2.
And dry-mixed. Each of these mixtures is φ10m
m, and formed into a pellet having a thickness of 1 mm under pressure. The products were reacted and sintered in air or oxygen at 720 to 820 ° C. on alumina boats, respectively, to prepare a body oxide material of the present invention.
この様に作成した夫々の酸化物を4Kから100Kの温度範
囲で超伝導性を測定した。その結果を下記第１表に示し
た。ここで分析の性能上酸素の値には±２割程度の誤差
が入る。The superconductivity of each oxide thus prepared was measured in a temperature range of 4K to 100K. The results are shown in Table 1 below. Here, due to the performance of the analysis, an error of about ± 20% is included in the value of oxygen.
第１表より明らかな様に、本発明の酸化物材料は良い
超伝導性を示している。更にサンプルNo.1の試料をEPM
A、TEM、XD分析した結果、第１図示の様な構造を有して
いることが判明した。ここでＡ、Ｄが主にBiであり、
Ｂ、Ｃが主にSrであり、DO面のＯにはかなりの欠陥があ
った。尚、この図ではc/2の長さの分だけ構造を示して
いるが、全体的に本発明で言う構造となっている。As is clear from Table 1, the oxide material of the present invention shows good superconductivity. In addition, EPM
As a result of A, TEM, and XD analysis, it was found that it had a structure as shown in FIG. Here, A and D are mainly Bi,
B and C were mainly Sr, and O on the DO surface had considerable defects. In this figure, the structure is shown only for the length of c / 2, but it is the structure generally referred to in the present invention.
（効果） 以上説明した様に、本発明により以下の効果が得られ
る。 (Effects) As described above, the following effects can be obtained by the present invention.
（１）超伝導転移温度も液状ヘリウム温度（4.2K）より
も30K以上高いので、比較的手軽に且つ安定的に超伝導
材料として使用できる。(1) Since the superconducting transition temperature is 30K or more higher than the liquid helium temperature (4.2K), it can be used relatively easily and stably as a superconducting material.
（２）焼成温度が720℃でもよく、従来のものより100℃
以上も低く焼成温度を抑えることが出来る。これは薄膜
化及び線材化の時にも有利である。(2) The firing temperature may be 720 ° C, which is 100 ° C higher than the conventional one.
The sintering temperature can be suppressed as low as above. This is also advantageous when thinning and forming a wire.
（３）重金属であるBiはTlの比を、従来のBi2Sr2CanCu
1+nOy等に比べて数十％も下げられ、材料作成上及び使
用上の安全性が高められた。(3) Bi, which is a heavy metal, determines the ratio of Tl to the conventional Bi 2 Sr 2 Ca n Cu
Compared to 1 + n O y etc., it was reduced by several tens of percent, and the safety in material preparation and use was improved.
（４）低温及び短時間の焼成でも良好な超電導持性が得
られ、又、パッキングデンシティーの高い製造のものが
得られた。(4) Good superconductivity was obtained even at low temperature and short time firing, and a product having a high packing density was obtained.
第１図は本発明の酸化物の構造を図解的に説明する図で
ある。FIG. 1 is a diagram schematically illustrating the structure of the oxide of the present invention.
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C01G 1/00 ZAAContinuation of front page (58) Field surveyed (Int.Cl. 6 , DB name) C01G 1/00 ZAA
Claims (1)
層状の酸化物材料において、ｃ軸に沿って順にAO面、AO
面、BO面、CuO2面、CO面、DO面、CO面、CuO2面、BO面、
AO面となる周期構造を有し、上記Ａ及びＤが、Bi及びTl
からなる元素群から選ばれた１種以上の元素又は原子団
であり、Ｂ及びＣがSr及びBaからなる元素群から選ばれ
た１種以上の元素又は原子団であることを特徴とする金
属酸化物材料。1. A layered oxide material comprising a plane having an atomic arrangement perpendicular to the c-axis, wherein an AO plane and an AO plane are sequentially arranged along the c-axis.
Plane, BO plane, CuO 2 plane, CO plane, DO plane, CO plane, CuO 2 plane, BO plane,
It has a periodic structure that becomes an AO plane, and A and D are Bi and Tl
A metal, wherein B and C are one or more elements or atomic groups selected from the element group consisting of Sr and Ba. Oxide materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1307440A JP2781033B2 (en) | 1989-11-29 | 1989-11-29 | Metal oxide material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1307440A JP2781033B2 (en) | 1989-11-29 | 1989-11-29 | Metal oxide material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03170329A JPH03170329A (en) | 1991-07-23 |
| JP2781033B2 true JP2781033B2 (en) | 1998-07-30 |
Family
ID=17969101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1307440A Expired - Fee Related JP2781033B2 (en) | 1989-11-29 | 1989-11-29 | Metal oxide material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2781033B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01242459A (en) * | 1988-03-23 | 1989-09-27 | Semiconductor Energy Lab Co Ltd | Superconducting ceramics |
-
1989
- 1989-11-29 JP JP1307440A patent/JP2781033B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 日経超電導、１９８８−２−２２付 第４号，Ｐ．２〜４ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03170329A (en) | 1991-07-23 |
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